AND METHODS OF MAKING SAME

TECHNICAL FIELD

This disclosure relates to recycled or brown paper board and methods of making same, and more particularly to coatings based on copolymer dispersions for use in recycled or brown paper board.

BACKGROUND

Emulsion binders based on vinyl acetate (e.g. EVA) or copolymers of vinyl acetate and butyl acrylate are known to provide desirable light scattering in coated paper board such as recycled or brown paper board. The light scattering in the paper board coating is provided by the combination of the binders, fillers such as mineral pigments, and air voids in the coating. The coatings also provide a surface that allows the recycled and brown board to be printed upon, which is common, for instance, in paper board used for packaging. Although the vinyl acetate- butyl acrylate copolymers and EVA copolymers can provide good coverage (opacity), a large amount of the binder has to be used to provide the necessary amount of print strength to result in good printing quality and to prevent "picking" from occurring.

Recycled and brown paper board coatings also generally include a significant amount of titanium dioxide as it increases the overall opacity in the paper coating. Unfortunately, titanium dioxide is expensive and thus there is a desire to reduce the amount of titanium dioxide used in paper board coatings.

SUMMARY

Recycled or brown paper board is provided having a surface with a coating having one or more layers, at least one layer of the coating comprising one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof, wherein the average Tg of the one or more copolymers present in the coating layer is 25°C or greater and the average polymer particle size of the one or more copolymers used in the coating layer is 130 nm or greater. In some embodiments, the coating comprises two or more layers. In some embodiments, the coating layer can be the layer of the coating that is furthest from said surface (the outermost layer). The one or more copolymers used in the coating layer can have an average polymer particle size of from 140 nm to 220 nm or from 150 nm to 200 nm. 2

In some embodiments, the coating layer comprises more than one copolymer selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof, e.g., at least one styrene-acrylic-based copolymer and at least one styrene- butadiene-based copolymer. In some embodiments, the coating can include a layer including a styrene-acrylic-based copolymer and a styrene-butadiene-based copolymer. In some embodiments, each of the coating layers includes one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof, wherein the average Tg of the one or more copolymers present in the coating layers is 25°C or greater and the average polymer particle size of the one or more copolymers used in the coating layers is 130 nm or greater. In some embodiments, the coating comprises at least one layer comprising a styrene-acrylic-based copolymer and at least one layer comprising a styrene- butadiene-based copolymer. For example, the coating can include a first layer adjacent the paper board comprising a styrene-butadiene-based copolymer and a second layer adjacent the first layer comprising a styrene-acrylic-based copolymer. Alternatively, the coating can include a first layer adjacent the paper board comprising a styrene-acrylic-based copolymer and a second layer adjacent the first layer comprising a styrene-acrylic-based copolymer. In some embodiments, the coating comprises at least one styrene-acrylic-based copolymer or styrene-butadiene- based latex copolymer having a Tg of 25°C or greater and at least one styrene-acrylic-based copolymer or styrene-butadiene-based copolymer having a Tg less than 25°C. The coating can consist essentially of one or more copolymers selected from the group consisting of styrene- acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof. At least one of the one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof can be further derived from (meth)acrylonitrile.

The outermost coating layer for the recycled paper board or brown paper board can include less than 10% by weight titanium dioxide on a dry basis based on total amount of filler in the coating layer. In some embodiments, the overall solids content in the coating or a coating layer is greater than 30%. The uncoated recycled paper board or brown paper board can have a TAPPI brightness of from 20 to 50. In some embodiments, the board is a Kraft unbleached brown board. The coated recycled paper board or brown paper board can have Prufbau passes to fail of 5 or greater using the Prufbau test method.

Also provided is a method of producing a coated recycled paper board or brown paper board, comprising applying a coating in one or more layers to a surface of the recycled paper board or brown paper board, at least one layer of the coating comprising one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof, wherein the average Tg of the one or more copolymers present in the coating layer is 25°C or greater and the average polymer particle size of the one or more copolymers present in the coating layer is 130 nm or greater; and allowing the coating to dry onto the surface of the recycled paper board or brown paper board. In some embodiments, the applying step comprises applying the coating in two or more layers to the surface. For ex- ample, the applying step can include applying a first coating layer adjacent the paper board comprising one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof and then applying a second coating layer adjacent the first coating layer comprising one or more copolymers including a styrene-acrylic-based copolymer, wherein the average Tg of the one or more copolymers present in the second coating layer is 25°C or greater and the average polymer particle size of the one or more copolymers present in the second coating layer is 130 nm or greater. The average Tg of the one or more copolymers present in the first coating layer can also be 25 °C or greater and/or the average polymer particle size of the one or more copolymers present in the first coating layer can be 130 nm or greater. In some embodiments, the coating comprises more than one copolymer selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof, e.g., at least one styrene-acrylic-based copolymer and at least one styrene-butadiene-based copolymer. For example, the coating or a coating layer can include at least one styrene-acrylic-based copolymer or styrene-butadiene-based latex copolymer having a Tg of 25°C or greater and at least one styrene-acrylic-based copolymer or styrene-butadiene- based copolymer having a Tg less than 25°C. In some embodiments, the copolymer in the coating consists essentially of one or more copolymers selected from the group consisting of styrene- acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof. In some embodiments, the at least one copolymer selected from the group consisting of styrene-acrylic- based copolymers, styrene-butadiene-based copolymers, and mixtures thereof can be further derived from (meth)acrylonitrile.

A coating composition for recycled paper board or brown paper board is also disclosed comprising one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof, wherein the average Tg of the one or more copolymers present in the coating composition is 25 °C or greater and the average polymer particle size of the one or more copolymers present in the coating composition is 130 nm or greater. In some embodiments, the average polymer particle size of the one or more copolymers is from 140 nm to 220 nm or from 150 nm to 200 nm. The coating composition can include more than one copolymer selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof. For example, the coating composition can include a styrene-acrylic-based copolymer or a styrene-butadiene-based latex copolymer having a Tg of 25°C or greater and a styrene-acrylic-based copolymer or a sty- rene-butadiene-based copolymer having a Tg less than 25°C. In some embodiments, the one or more copolymers consist essentially of one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof. At least one of the one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof can be further derived from (meth)acrylonitrile. The coating for the recycled paper board or brown paper board can include less than 10% by weight titanium dioxide on a dry basis based on total amount of filler in the coating. In some embodiments, the overall solids content in the coating is greater than 30%.

The details of one or more embodiments are set forth in the description below. Other fea- tures, objects, and advantages will be apparent from the description and from the claims.

DETAILED DESCRIPTION

Recycled or brown paper board is provided having a surface with a coating having one or more layers, at least one layer of the coating comprising one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof. The uncoated recycled paper board or brown paper board can have a TAPPI brightness of from 20 to 50 using TAPPI Test T452. In some embodiments, the recycled or brown board is unbleached, i.e., it has not undergone any bleaching process. In some embodiments, the board is a brown board such as a Kraft unbleached brown board.

At least one of the coating layers comprises one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof. In some embodiments, the coating or a coating layer comprises more than one copolymer selected from the group consisting of styrene-acrylic-based copolymers, styrene- butadiene-based copolymers, and mixtures thereof. For example, the coating or a coating layer can include at least one styrene-acrylic-based copolymer and at least one styrene-butadiene- based copolymer, two styrene-butadiene-based copolymers, or two styrene-acrylic-based copolymers. Of the polymers present in the coating or a coating layer, there can be greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than butadiene-based copolymers, or mixtures thereof. In some embodiments, the polymers in the coating or a coating layer can consist essentially of or consist of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, or mixtures thereof.

In some embodiments, the coating comprises two or more layers (e.g., two or three layers) applied to the surface of the recycled paper board or brown paper board. The coating layers can

7 7 7 be applied in an amount of from 5 to 25 g/m , from 7 to 20 g/m or from 10 to 15 g/m per layer. In some embodiments, the outermost layer includes one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof. The one or more copolymers in the outermost layer can have an average Tg of 25°C or greater and/or the average polymer particle size of the one or more copolymers can be 130 nm or greater. The layers can each include at least one styrene-acrylic-based copolymer, at least one styrene-butadiene-based copolymer, or a mixture thereof or a majority of the layers can include at least one styrene-acrylic-based copolymer, at least one styrene-butadiene-based copolymer, or a mixture thereof (e.g. two out of three layers). In some embodiments, the coating can comprise a first layer adjacent the paper board comprising one or more copolymers selected from the group consisting of styrene-acrylic-based copolymers, styrene-butadiene-based copolymers, and mixtures thereof, and a second layer adjacent the first layer comprising a styrene- acrylic-based copolymer. For example, the first layer can include at least one styrene-acrylic- based copolymer, at least one styrene-butadiene-based copolymer, or a blend of styrene-acrylic- based and styrene-butadiene-based copolymers. In some embodiments, the copolymers used in the first and second layers are the same or the coating compositions used in the first and second layers are the same.

The coating or a coating layer comprises one or more copolymers selected from the group consisting of styrene-acrylic-based and styrene-butadiene-based copolymers wherein the average glass transition temperature (Tg) of the copolymers present in the coating is 25 °C or greater.

The average Tg is weighted based on the amount of the polymer included in the coating or coating layer. For example, if a coating layer includes 25% of a first copolymer having a Tg of 20°C and 75% of a second copolymer having a Tg of 60°C, the average Tg would be (.25)(20°C) + (.75)(60°C) or 50°C. The average Tg can be greater than 25°C, 26°C or greater, 27°C or greater, 28°C or greater, 29°C or greater, or 30°C or greater, or can be 60°C or less, 55°C or less, 50°C or less, 45°C or less, 40°C or less, or 35°C or less. In some embodiments, the coating or a coating layer comprises at least one styrene-acrylic-based copolymer or styrene-butadiene-based latex copolymer having a Tg of 25°C or greater (e.g., from 25°C to 100°C, 30°C to 75°C or 35°C to 65°C) and at least one styrene-acrylic-based copolymer or styrene-butadiene-based copolymer having a Tg less than 25°C (e.g., from -5°C to less than 25°C, 0°C to 20°C or 5°C to 15°C). In some embodiments, the coating can comprise a first layer adjacent the paper board comprising a styrene-acrylic-based copolymer or a styrene-butadiene-based copolymer having a Tg of 25°C or greater and a second layer adjacent the first layer comprising a styrene-acrylic-based copolymer or a styrene-butadiene-based copolymer having a Tg of 25°C or greater, or vice versa. The Tg can be measured using differential scanning calorimetry (DSC).

In some embodiments, the coating includes a styrene-acrylic-based copolymer having a Tg of 25°C or greater. The styrene-acrylic-based copolymer can be derived from styrene and one or more (meth)acrylate monomers in an amount of 80% or greater, 85% or greater, 90% or greater, or 95% or greater, of the total monomer weight. As used herein, the term

"(meth)acrylate" includes both acrylates and methacrylates. The (meth)acrylates can include esters of α,β-monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 6 carbon atoms with alkanols having 1 to 12 carbon atoms (e.g., esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid, or itaconic acid, with Ci-C] 2, Ci-C ₈ , or C 1 -C4 alkanols such as ethyl, n-butyl, isobutyl and 2-ethylhexyl acrylates and methacrylates, dimethyl maleate and n-butyl maleate). Examples of (meth)acrylate monomers suitable for use in the styrene-acrylic-based copolymers include butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, methyl methacrylate, and methyl acrylate. In some embodiments, the styrene-acrylic-based copolymer is derived from 60% or greater, 65% or greater, 70% or greater, 75% or greater, or 80% or greater styrene. The styrene-acrylic-based copolymer can be derived from the (meth)acrylate in an amount of 5%- 30% or 10%-25%. In some embodiments, the (meth)acrylate includes butyl acrylate. The styrene-acrylic-based copolymer can further derived from (meth)acrylonitrile, for example, in an amount of greater than 0% to 30%, 3 to 25% or 5% to 20% (e.g. 15%). In some embodiments, the copolymer can be derived from acid-based monomers (e.g. α,β-monoethylenically unsatu- rated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, dimethacrylic acid, ethylacrylic acid, allylacetic acid, vinylacetic acid maleic acid, fumaric acid, mesaconic acid, methylenemalonic acid, and citraconic acid) in an amount of greater than 0% to 10% (e.g. 0.5% to 6% or 2% to 5%). In some embodiments, the copolymer includes itaconic acid and optionally acrylic acid. In some embodiments, the copolymer can be derived from (meth)acrylamide in an amount of greater than 0% to 5% (e.g. 0.5 to 3%). In some embodiments, the styrene-acrylic-based copolymer can include a small amount of butadiene, e.g., less than 5%. As would be understood to one skilled in the art, the coating could also include a styrene-acrylic-based copolymer having a Tg of less than 25°C. „

7

In some embodiments, the coating includes a styrene-butadiene-based copolymer having a Tg of 25°C or greater. The styrene-acrylic-based copolymer can be derived from styrene and butadiene in an amount of 80% or greater, 85% or greater, 90% or greater, or 95% or greater, of the total monomer weight. In some embodiments, the styrene-butadiene-based copolymer is derived from 60% or greater, 65% or greater, 70% or greater, 75% or greater, or 80%) or greater styrene. The styrene-butadiene-based copolymer can be derived from 1 ,3-butadiene in an amount of 5%>-35% or 10%>~30%. The styrene-butadiene-based copolymer can further derived from (meth)acrylonitrile, for example, in an amount of greater than 0% to 25%, 2% to 20% or 5% to 15% (e.g. 10%). In some embodiments, the copolymer can be derived from acid-based monomers (e.g. α,β-monoethylenically unsaturated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, dimethacrylic acid, ethylacrylic acid, ally- lacetic acid, vinylacetic acid maleic acid, fumaric acid, mesaconic acid, methylenemalonic acid, and citraconic acid) in an amount of greater than 0% to 10%o (e.g. 0.5% to 5%). In some embodiments, the copolymer includes itaconic acid and optionally acrylic acid. In some embodi- ments, the copolymer can be derived from (meth)acrylamide in an amount of greater than 0% to 5% (e.g. 0.5 to 3%). In some embodiments, the styrene-butadiene-based copolymer can include a small amount of a (meth)acrylate, e.g., less than 10% or less than 5%. As would be understood to one skilled in the art, the coating could also include a styrene-butadiene-based copolymer having a Tg of less than 25°C.

The styrene-acrylic-based copolymers and/or styrene-butadiene-based copolymers can further include additional monomers. Exemplary monomers include other vinylaromatic compounds (e.g., a-methylstyrene, o-chlorostyrene, and vinyltoluenes); 1,2-butadiene, isoprene; anhydrides of α,β-monoethylenically unsaturated mono- and dicarboxylic acids (e.g., maleic anhydride, itaconic anhydride, and methylmalonic anhydride); other alkyl-substituted acrylamides (e.g., N-tert-butylacrylamide and N-methyl(meth)acrylamide); vinyl and vinylidene halides (e.g., vinyl chloride and vinylidene chloride); vinyl esters of CI -CI 8 mono- or dicarboxylic acids (e.g., vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate); C1-C4 hydroxyalkyl esters of C3-C6 mono- or dicarboxylic acids, especially of acrylic acid, methacrylic acid or maleic acid, or their derivatives alkoxylated with from 2 to 50 moles of eth- ylene oxide, propylene oxide, butylene oxide or mixtures thereof, or esters of these acids with CI -CI 8 alcohols alkoxylated with from 2 to 50 mol of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof (e.g., hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and methylpolyglycol acrylate); and monomers containing glycidyl groups (e.g., glycidyl methacry- late). g

Additional monomers suitable for use in the copolymers include linear 1 -olefins, branched-chain 1-olefms or cyclic olefins (e.g., ethene, propene, butene, isobutene, pentene, cyclopentene, hexene, and cyclohexene); vinyl and allyl alkyl ethers having 1 to 40 carbon atoms in the alkyl radical, wherein the alkyl radical can possibly carry further substituents such as a hydroxyl group, an amino or dialkylamino group, or one or more alkoxylated groups (e.g., methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl cyclohexyl ether, vinyl 4 -hydroxy butyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-(diethylamino)ethyl vinyl ether, 2-(di-n-butylamino)ethyl vinyl ether, methyldiglycol vinyl ether, and the corresponding allyl ethers); sulfo-functional monomers (e.g., allylsulfonic acid, methallylsulfonic acid, styrenesulfonate, vinylsulfonic acid, allyloxybenzene- sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their corresponding alkali metal or ammonium salts, sulfopropyl acrylate and sulfopropyl methacrylate); vinylphosphonic acid, dimethyl vinylphosphonate, and other phosphorus monomers; alkylaminoalkyl (meth)acrylates or alkylaminoalkyl(meth)acrylamides or quaternization products thereof (e.g., 2-(N,N- dimethylamino)ethyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-(N,N,N- trimethylammonium)ethyl (meth)acrylate chloride, 2-dimethylaminoethyl(meth)acrylamide, 3- dimethylaminopropyl(meth)acrylamide, and 3-trimethylammoniumpropyl(meth)acrylamide chloride); allyl esters of C1-C30 monocarboxylic acids; N- Vinyl compounds (e.g., N- vinylformamide, N-vinyl-N-methylformamide, N-vinylpyrrolidone, N-vinylimidazole, 1-vinyl- 2-methylimidazole, l-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinylcarbazole, 2- vinylpyridine, and 4-vinylpyridine); monomers containing 1 ,3-diketo groups (e.g., acetoace- toxyethyl(meth)acrylate or diacetonacrylamide; monomers containing urea groups (e.g., urei- doethyl (meth)acrylate, acrylamidoglycolic acid, and methacrylamidoglycolate methyl ether); and monomers containing silyl groups (e.g., trimethoxysilylpropyl methacrylate).

Suitable monomers can also include one or more crosslinkers such as N-alkylolamides of α,β-monoethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms and esters thereof with alcohols having 1 to 4 carbon atoms (e.g., N-methylolacrylamide and N- methylolmethacrylamide); glyoxal based crosslinkers; monomers containing two vinyl radicals; monomers containing two vinylidene radicals; and monomers containing two alkenyl radicals. Exemplary crosslinking monomers can include diesters of dihydric alcohols with α,β- monoethylenically unsaturated monocarboxylic acids, of which in turn acrylic acid and methacrylic acid can be employed. Examples of such monomers containing two non-conjugated ethylenically unsaturated double bonds can include alkylene glycol diacrylates and dimethacry- lates, such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1 ,4-butylene glycol dia- crylate and propylene glycol diacrylate, divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate and methylenebisacrylamide. In some embodiments, the crosslinking monomers can include alkylene glycol diacrylates and di- methacrylates, and/or divinylbenzene. The crosslinking monomers when used in the copolymer can be present in an amount of from 0.2 to 5 phm ("parts per hundred monomer") and are considered part of the total amount of monomers used in the copolymer.

Additional monomers can include copolymerizable surfactants present in the copolymer in an amount of from 0.5% to 5%, or 1% to 4% by weight. Suitable copolymerizable surfactants are described in U.S. Patent No. 6,841,655, which is hereby incorporated by reference in its en- tirety. For example, ADEKA REASOAP SR-10, which includes ammonium salts of poly(oxy- 1 ,2-ethanediyl),alpha-sulfo-omega-[ 1 -(hydroxymethyl)-2-(2-propenyloxy)ethoxy]-, C 11 -rich, Cl O-14-branched alkyl ethers, can be used. Exemplary copolymerizable surfactants in which R ¹ is C7-C1 1 alkyl-phenyl can include ADEKA REASOAP series NE and SE surfactants, such as NE-10, NE-20, NE-30, NE-40, NE-50, SE-10N, SE-20N, and SE-1025N.

In some embodiments, small amounts (e.g., from 0.01 to 4 phm) of molecular weight regulators, such as tert-dodecyl mercaptan, can be used. Such regulators can be added to the polymerization zone in a mixture with the monomers to be polymerized and are considered part of the total amount of monomers used in the copolymer.

The average polymer particle size of the copolymers present or used in the coating or a coating layer is 130 nm or greater. The average polymer particle size of the polymers in the coating or a coating layer can be determined by determining the average particle size of the polymer particles in the dispersions used in the coating and then determining the average based on the amount of each copolymer used in the coating. The average particle size can be measured using laser diffraction methods (e.g., by using a NICOMP instrument). For example, if the coat- ing has two layers with one layer including 75% of the total amount of polymer in the coating and the average polymer particle size of the coating used in the first layer is 120 nm and the second layer includes 25%» of the total amount of polymer in the coating and the average polymer particle size of the coating used in the second layer is 180 nm, the average polymer particle size for the copolymers present in the coating would be (0.75)(120 nm) + (0.25)(180 nm) or 135 nm. For a coating layer, the average particle size would just be determined by determining the average particle size of the polymers used in the coating composition for the coating layer. In some embodiments, the average polymer particle size of the copolymers present or used in the coating or a coating layer is 130 nm or greater, 135 nm or greater, 140 nm or greater, 145 nm or greater, 150 nm or greater, 155 nm or greater, or 160 nm or greater or 220 nm or less, 215 nm or less, 210 nm or less, 205 nm or less, or 200 nm or less. In some embodiments, the styrene-acrylic- based copolymer or styrene-butadiene-based copolymer in the coating or a coating layer, or all the styrene-acrylic-based copolymers or styrene-butadiene-based copolymers in the coating or a coating layer, have an average polymer particle size of 130 nm or greater (e.g., 135 nm or greater, 140 nm or greater, 145 nm or greater, 150 nm or greater, 155 nm or greater, or 160 nm or greater or 220 nm or less, 215 nm or less, 210 nm or less, 205 nm or less, or 200 nm or less).

The copolymer emulsion can be prepared by polymerizing the monomers using free- radical aqueous emulsion polymerization. The emulsion polymerization temperature is generally from 30 to 95°C or from 75 to 90°C. In some embodiments, the polymerization medium is an aqueous medium. The emulsion polymerization can be carried out either as a batch, semi-batch or continuous process. Typically, a semi-batch process is used. In some embodiments, a portion of the monomers can be heated to the polymerization temperature and partially polymerized, and the remainder of the polymerization batch can be subsequently fed to the polymerization zone continuously, in steps or with superposition of a concentration gradient.

The free-radical emulsion polymerization can be carried out in the presence of a free- radical polymerization initiator. The free-radical polymerization initiators that can be used in the process are all those which are capable of initiating a free-radical aqueous emulsion polymerization including alkali metal peroxydisulfates and H2O2, or azo compounds. Combined systems can also be used comprising at least one organic reducing agent and at least one peroxide and/or hydroperoxide, e.g., tert-butyl hydroperoxide and the sodium metal salt of hydroxymethane- sulfinic acid or hydrogen peroxide and ascorbic acid. Combined systems can also be used additionally containing a small amount of a metal compound which is soluble in the polymerization medium and whose metallic component can exist in more than one oxidation state, e.g., ascorbic acid/iron(II) sulfate/hydrogen peroxide, where ascorbic acid can be replaced by the sodium metal salt of hydroxymethanesulfinic acid, sodium sulfite, sodium hydrogen sulfite or sodium metal bisulfite and hydrogen peroxide can be replaced by tert-butyl hydroperoxide or alkali metal peroxydisulfates and/or ammonium peroxydisulfates. In general, the amount of free-radical initiator systems employed can be from 0.1 to 2 phm, based on the total amount of the monomers to be polymerized. In some embodiments, the initiators are ammonium and/or alkali metal peroxydi- sulfates (e.g., sodium peroxydisulfates), alone or as a constituent of combined systems. The manner in which the free-radical initiator system is added to the polymerization reactor during the free-radical aqueous emulsion polymerization is not critical. It can either all be introduced into the polymerization reactor at the beginning, or added continuously or stepwise as it is consumed during the free-radical aqueous emulsion polymerization. In some embodiments, some of the initiator is introduced at the beginning and the remainder is added to the polymerization zone as it is consumed. It is also possible to carry out the free-radical aqueous emulsion polymerization under superatmospheric or reduced pressure.

The copolymer can be produced as a dispersion that includes, as a disperse phase, parti - cles of the copolymer dispersed in water. The copolymer dispersion can be prepared with a total solids content of from 10 to 75% by weight, 15 to 65% by weight, or 20 to 60% by weight. The copolymer dispersion can then be concentrated if desired to provide a total solids content of 40- 75% by weight.

The polymer dispersions described herein can be combined with one or more fillers (e.g., mineral fillers and/or coating pigments) to produce a coating composition for recycled paper board or brown paper board. Mineral fillers generally have a substantial proportion of particles having a particle size greater than 2 microns whereas coating pigments have a substantial proportion of particles having a particle size less than 2 microns. In some embodiments, the mineral fillers and/or coating pigments can be added to impart certain properties to a paper such as smoothness, whiteness, increased density or weight, decreased porosity, increased opacity, flatness, glossiness, and the like. The mineral fillers and/or coating pigments can include calcium carbonate (precipitated or ground), kaolin, clay, talc, diatomaceous earth, mica, barium sulfate, magnesium carbonate, vermiculite, graphite, carbon black, alumina, silicas (fumed or precipitated in powders or dispersions), colloidal silica, silica gel, titanium oxides (e.g. titanium diox- ide), aluminum hydroxide, aluminum trihydrate, satine white, and magnesium oxide. The formulation can include exclusively mineral fillers or coating pigments but generally includes a blend of mineral fillers and coating pigments (e.g. weight ratios of 90: 10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80 or 10:90). Exemplary coating pigments include titanium dioxide coating pigments, MIRAGLOSS 91 (a kaolin clay coating pigment commercially available from BASF Corporation), LOPAQUE M (a kaolin clay coating pigment commercially available from Thiele Kaolin Company), and HYDROCARB 90 (a calcium carbonate coating pigment commercially available from Omya Paper). Titanium dioxide filler is often used with recycled paper board to provide increased coverage or opacity. In some embodiments, the filler content for the coating or a coating layer for the recycled paper board includes 90% clay (e.g. kaolin) and 10% titanium dioxide. In some embodiments, the coating or a coating layer (e.g. the outermost layer) for the recycled paper board or brown paper board can include less than 10%, less than 9%, less than 8%o, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or 0% by weight titanium dioxide based on the total amount of filler used in the coating. In some embodiments, wherein the coating has two or more layers, the coating can include coarse fillers (e.g. mineral fillers) in the first layer applied to the surface of the paper board (the basecoat) and fine fillers (e.g. coating pigments) in the second layer applied to the first layer (the topcoat).

In some embodiments, the coating composition can include one or more dyes and/or col- ored pigments to produce a colored or patterned paper or to change the shade of the paper. Exemplary dyes can include basic dyes, acid dyes, anionic direct dyes, and cationic direct dyes. Exemplary colored pigments include organic pigments and inorganic pigments in the form of anionic pigment dispersions and cationic pigment dispersions.

In some embodiments, one or more thickeners (rheology modifiers) can be added to in- crease the viscosity of the coating composition. Suitable thickeners can acrylic copolymer dispersions sold under the STEROCOLL and LATEKOLL trademarks from BASF Corporation, Florham Park, NJ, hydroxyethyl cellulose, guar gum, jaguar, carrageenan, xanthan, acetan, kon- jac, mannan, xyloglucan, urethanes and mixtures thereof. The thickeners can be added to the coating formulation as an aqueous dispersion or emulsion, or as a solid powder.

The coating composition described herein can include additives such as dispersants, initiators, stabilizers, chain transfer agents, buffering agents, salts, preservatives, fire retardants, wetting agents, protective colloids, biocides, corrosion inhibitors, crosslinkers, crosslinking promoters, and lubricants. Exemplary dispersants can include sodium polyacrylates in aqueous solution such as those sold under the DARVAN trademark by R.T. Vanderbilt Co., Norwalk, CT.

The coating described herein or a coating layer can include greater than 30% solids by weight. For example, the coating or a coating layer can include greater than 35%, greater than 40%), greater than 45%, greater than 50%, greater than 55%, or greater than 60% solids, or less than 90%, less than 85%, less than 80%, less than 75%, or less than 70% solids by weight. In some embodiments, if the coating includes more than one layer, each layer of the coating can include greater than 30% solids.

The amount of filler in the coating or a coating layer can be from 60% to 95% by weight of the coating or a coating layer on a dry basis. For example, the coating or a coating layer can include can include 60% or greater, 65% or greater, or 70% or greater filler, and/or 95% or less 92.5% or less, or 90% or less filler by weight on a dry basis.

With regard to solid content of the coating or a coating layer, the copolymer can be present in an amount of 4 to 20 wt%, 6 to 18 wt%, or 8 to 16 wt% of the solid content of the coating. A thickener can be present in an amount of 0 to 5 wt%, greater than 0 to 3 wt%, or greater than 0 to 1 wt% of the solid content of the coating or a coating layer. Dyes and colored pigments can be present in an amount of 0 to 3 wt%, 0 to 2 wt%, or 0 to 1 wt% of the solid content of the coating or a coating layer. Other additives can be present in an amount of 0 to 5 wt%, 0 to 3 wt%, or 0 to 1 wt% of the solid content of the coating or a coating layer.

Also provided is a method of producing a coated recycled paper board or brown paper board, comprising applying a coating in one or more layers to a surface of the recycled paper board or brown paper board. The coating can be applied in one or more layers to the recycled paper board or brown paper board, for example, by using any known method such as an air knife, blade coating, roll coating, or a metered size press. The paper coating formulation can be provided on the paper board in an amount of 5-25 g/m per layer. In some embodiments, the coating composition can be applied in an amount of less than 20% by weight or 5 to 15% by weight based on the weight of the coated paper board.

In some embodiments, the coated recycled paper board or brown paper board can have Prufbau passes to fail of 5 or greater, 6 or greater or 7 or greater.

In some embodiments, the coating composition described herein can have a water retention capacity (AAGWR at 2 ATMs for 2 minutes) of 100 g/m ² or less, 90 g/m ² or less, or 80

2

g/m or less, when the formulation is applied to paper.

In some embodiments, the coating composition described herein can have an immobilization time of 100 sec or longer, 200 sec or longer, 300 sec or longer, 400 sec or longer, 500 sec or longer, or 600 sec or longer, as measured according to the method described in N. Willenbacher, et al, "New Laboratory Test to Characterize Immobilization and Dewatering of Paper Coating Colors" TAPPI Journal 82(8), 1999, pp 167-174.

The coatings described herein based on styrene-acrylic copolymers, styrene-butadiene copolymers, or mixtures thereof, provide a desirable amount of print strength without the need to provide as much of the copolymer in the coating as is typically used with vinyl acetate based copolymers used in the prior art. Thus, even when less of the copolymer is used than in typical with vinyl acetate based copolymers, the printing performance is improved. The coatings also provide good coverage/opacity to the recycled or brown paper board, even when less titanium dioxide is used compared to prior art coatings. The reduction in the amount of binder and titanium dioxide used in the coatings desirable reduces the cost of the coating.

PROCEDURES The Prufbau test method - Prufbau passes to fail measured according to the procedure below.

a. Prepare the sample (paper or paperboard) by allowing it to condition for 24 hours at 72°F ± 5°F and a relative humidity of 50% ± 5%.

b. Cut samples to measure approximately 240 mm + 2 mm by 47 + 0.5 mm. If the sample is too wide, it may interfere with the run through the apparatus. If the sample is too narrow, it may result in the sample running off sideways, or askew.

c. Place the sample under clip located at the end of the sample carrier and fold sample back 180° so that it lies flat and parallel on the carrier with the side to be tested upper - most. Secure the free end with tape. Do not allow fingerprints to contaminate the portion of the sample to be tested.

d. The mounted sample is placed in the track before the printing station (multipurpose print test machine - system Dr. Druner - Prufbau) and a 4 cm wide aluminum printing disc installed. The carrier should have the clip to the rear, so that the taped end of the sample is printed first.

e. Print the sample at a printing pressure of 800 N and a printing speed of 1 m/s. Use 0.3 ml ink per sample, a distribution time of 30 seconds, and a printing form inking time of 30 seconds.

f. With the same printing disc, after a 10 second pause, print again. Please note the length of the pause may be adjusted to achieve desired pick. Do not clean the disc between printings.

g. After another pause of the same duration, print the sample again. The sample is either printed a certain number of times or until it begins to pick, in which case the number of impressions is noted.

h. The number of impressions that are made when picking occurs is noted. If picking does not occur on the last impression, the symbol > and the number of the last impression is noted. Note: through progressive drying on both the paper and the printing disc, the ink becomes tackier. The paper is then subject to increasing force from print to print. The more closed the coating is against the fluid portion of the ink (i.e., the slower the rise in the ink's vis- cosity), the more passes are possible before picking begins.

EXAMPLES The following non-limiting examples are provided to more fully illustrate some particular embodiments. Parts and percentages are provided on a per weight basis except as otherwise indicated. Comparative Examples 1-2 and Examples 1-3

Coating formulations were prepared by combining the following ingredients:

PPH = parts per hundred by weight of pigment

2LOPAQUE M pigment available from Thiele Kaolin Company

3DISPEX NV40 dispersant available from BASF Corporation

4STEROCOLL FS thickener available from BASF Corporation

⁵ CALSAN 50 lubricant available from BASF Corporation

The pH was adjusted to 8.5 for each formulation using NaOH and the total solids percent was adjusted to 60%. For Comparative Example 1, the copolymer was a styrene/butyl acry- late/acrylonitrile copolymer having a Tg of 6°C and an average particle size of 200 nm. For Comparative Example 2, the copolymer was POLYCO 3103, a vinyl acetate/butyl acrylate copolymer commercially available from Rohm & Haas having a Tg of 29°C and an average particle size of 242 nm. For Example 1, the copolymer was a styrene/butyl acrylate copolymer having a Tg of 25°C and an average particle size of 130 nm. For Example 2, the copolymer was a styrene/butyl acrylate/itaconic acid/acrylic acid copolymer having a Tg of 25°C and an average particle size of 190 nm. For Example 3, the copolymer was a styrene/butyl acrylate /itaconic acid copolymer having a Tg of 25°C and an average particle size of 190 nm. The coatings were applied using a Modern Metalcraft Lab Coater ISO # PAT-W0705 in two layers to the recycled paper board, each at a coating weight of 12 g/m (dry basis). The TAPPI brightness for the coated recycled paper board using each coating was determined by taking the average of 15 different brightness measurements and is provided in Figure 1. As shown in Figure 1, the copoly- mers including an acid and a larger particle size of 190 nm were comparable to the POLYCO 3103 in brightness.

Comparative Examples 3-4 and Examples 4-6

Additional coatings were prepared and applied to recycled paper board in the manner described above. Example 4 included a styrene/butyl aery 1 ate/acr y 1 on i t ri 1 e copolymer having a Tg of 38°C and an average particle size of 140 nm. Comparative Example 3 includes a styrene/butyl acrylate/acrylonitrile copolymer having a Tg of 6°C and an average particle size of 130 nm. Comparative Example 4 includes a styrene/butyl acrylate copolymer having a Tg of -20°C and an average particle size of 150 nm. Example 5 is a styrene/butadiene/itaconic acid/acrylic acid copolymer having a Tg of 65°C and an average particle size of 200 nm. Example 6 is a blend of 70% of the copolymer of Example 5 and 30% of a styrene/butadiene/itaconic acid/acrylic acid copolymer having a Tg of 6°C and an average particle size of 140 nm. Example 6 has an overall Tg of 47°C and an overall particle size of 180nm. Example 7 is a sty- rene/butyl acrylate copolymer having a Tg of 25°C and an average particle size of 200 nm. The TAPPI brightness for the coated recycled paper board using each coating was determined by taking the average of 15 different brightness measurements and is provided in Figure 2. As shown in Figure 2, the compositions based on copolymers or copolymer blends having a Tg of 25°C or greater and an average particle size of 130 nm or greater produced superior brightness values.

Examples 8-10

Additional coatings were prepared and applied to recycled paper board in the manner described above. Example 8 is a blend of 25% of the copolymer of Comparative Example 1 and 75% of the copolymer of Example 4 having an overall Tg of 30°C and an overall particle size of 155 nm. Example 9 is a blend of 50% of the copolymer of Comparative Example 1 and 50% of the copolymer of Example 4 having an overall Tg of 21°C and an overall particle size of 170 nm. Example 10 is a blend of 75% of the copolymer of Comparative Example 1 and 25% of the copolymer of Example 4 having an overall Tg of 13°C and an overall particle size of 185 nm. The TAPPI brightness for the coated recycled paper board using each coating was determined by taking the average of 15 different brightness measurements and is provided in Figure 3. Each of the coatings were tested a second time to verify the reproducibility of the data and are designated with "A" after the example. As shown in Figure 3, the compositions based on copolymers or copolymer blends having a Tg of 25°C or greater and an average particle size of 130 nm or greater produced good brightness values and these values were reproducible in subsequent tests.

Examples 1 1-14

Additional coatings were prepared and applied to recycled paper board in the manner described above. In Example 1 1 , the copolymer was a styrene/butyl acrylate copolymer having a Tg of 25°C and an average particle size of 200 nm. In Example 12, the copolymer was a styrene/butyl acrylate copolymer having a Tg of 25°C and an average particle size of 160 nm. In Example 13, the copolymer was a styrene/butyl acrylate copolymer prepared using 0.1 pph monomer of tert-dodecyl mercaptan molecular weight regulator, having a Tg of 25 °C, and an average particle size of 200 nm. Example 14 is a blend of 25% of the copolymer of Comparative Example 1 and 75% of the copolymer of Example 4 having an overall Tg of 30°C and an overall particle size of 155 nm. The contrast ratios for Comparative Example 2 and Examples 1 1-14 were measured using ASTM method D 6441-05 and are provided in Figure 4. Figure 5 illus- trates the number of Prufbau passes to fail for Comparative Example 2 and Examples 1 1 - 14 using the procedure described herein. As shown in Figures 4-5, the formulations for Examples 1 1- 14 had a good balance of opacity (as shown by the contrast ratio) and coating strength (as shown by the Prufbau passes to fail).

The compositions and methods described herein are not limited in scope by the embodi- ments disclosed herein which are intended as illustrations of a few aspects of the compositions and methods and any embodiments which are functionally equivalent are within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein will become apparent to those skilled in the art and are intended to fall within the scope of the appended claims. Further, while only certain representative combinations of monomers used to make a composition or method steps disclosed herein are specifically discussed in the embodiments above, other combinations of monomers used to make a composition or method steps will become apparent to those skilled in the art and also are intended to fall within the scope of the appended claims. The term "comprising" and variations thereof as used herein is used synonymously with the term "including" and variations thereof and are open, non- limiting terms. Although the terms "comprising" and "including" have been used herein to describe various embodiments, the terms "consisting essentially of and "consisting of can be used in place of "comprising" and "including" to provide for more specific embodiments and are also disclosed.